3-(coumarin-3-ylphenyl)-1,2,4-oxadiazol-5-yl ammonium salts

ABSTRACT

3-(COUMARIN - 3 - YLPHENYL)-1,2,5-OXADIAZOL-5-YL AMMONIUM SALTS WHICH MAY HAVE AN AKYL SUBSTITUENT AT THE 7 AND/OR 4 POSITION OF THE COUMARIN RING AND/OR A NONCHROMOPHORIC GROUP (E.G. HALOGEN, ALKYL OR ALKOXY) AT ANOTHER POSITION OF THE COUMARIN RING. THE COMPOUNDS ARE USEFUL IN THE WHITENING, BRIGHTENING AND/OR BLEACHING OF SYNTHETIC AND SEMI-SYNTHETIC FIBERS.

. 3,810,901 l S-(COUMARIN-Zl-YLPHENYL)-1,2,4 XADIAZOL S-YL AMMONIUM SALTS Hugh Davidson, Castleford, and Brian Ernest Le'ggetter, Wakefield, England, assignors to Hick'son 8t Welch Liin ited, Castleford, England No Drawing. Filed Feb. 10,-"1972, Ser. No; 225,336 Claims priority, application Great Britain, Feb 11, 19 71, 4,465/71 Int. Cl. (207d 85/52 its. Cl. 260-19358 13 Claims ABSTRACT OF THE DISCLOSURE 3-(conmarin 3. ylphenyl)-1,2,4-oxadiazol--yl ammonium salts which may have an alkyl substituent at the' 7 and/or 4 position ,of the coumarin ring and/or a nonchromophoric group (e.g. halogen, alkyl or alkoxy) at another position of the coumarin ring. 7 The compounds are usefulin the whitening,-brightening and/or bleaching of synthetic and semi-synthetic fibres.

This invention is concerned with new chemical'conipounds for use in the whitening, brightening and/or bleaching of synthetic and semi-synthetic materials in particular materials in the form-for example 'of textile yarns and fibres, synthetic resin sheets and the like.

Opticalwhitening agents have in recent' years found whereihR is a hydrogen atom or a substituted or unsub stitute'd alkyl group; R is a hydrogen atom orfajsubstituted or-un'substituted'alkyl group (e'.g., afmethylgroupfi R is a non-chromophoric group (e.g.," alhyd'ro'gen or halogen atom or a lower alkyl or alkoxy group); R4, R and -Rg 'are the same or different "and each is as a substituted or unsubstituted'alkyl group, R and R3 together with the adjacent nitrogen atom form a substituted or unsubstituted nitrogen-containing aromatic ring (e.g.'a pyridine ring), or two of R R and R together with the adjacentnitrogen atom form an aliphatic substituted or ill'l-fl substitutedheterocyclic ring (e.g. an aliphatic substituted or unsubstituted 5- or 6-membered heter'ocyclic'ring, such as piperidine; the ring may if desired contain a further hetero atom) with the remaining R R or R5 group being" a substituted or unsubstituted alkyl group; A is an alkylene or arylene group; m is 0 'or 1; X is the anion of an or ganic or inorganic acid, andn is the valency of the-said anion. t

Alkyl groups in atoms. R may for example ,be a loweralkyl or alkoxy synthetic andsemi-synthetic textile fibres and other mate the compounds of' the invention mayfor example be lower. alkyl groupshaving 1T6 carbon U d, SW 3mm 0" 3,810,901 Patented May 14, 1974 ring may contain oxygen as a further hetero atom and may be substituted for example by an alkyl group having 1-6 carbon atoms. Similarly, when R R and R and the-nitrogen atom represent an aromatic ring, the ring may be substituted by an alkyl group having 1-6 carbon atoms. A for example may be an alkylene group having 1-6 carbon atoms or a monocyclic arylene group such as a phenylene group.

Preferred are: Compounds wherein one or more of R R R R and R is an alkyl group having 1-6 carbon atoms; and/or R R and R form a nitrogen-containing heterocyclic ring which may be unsubstituted or substituted by an alkyl group having 1-6 carbon atoms; and/or A is an alkylene group having 1-6 carbon atoms or a monocyclic arylene group; t

Compounds wherein R is a methyl or ethyl group;

Compounds wherein R is a methyl group;

Compounds wherein R is a hydrogen or halogen atom or an alkyl or alkoxy group having 1-6 carbon atoms; such as those wherein R is a methoxy group;

Compounds wherein R R and R each is a methyl or ethyl group, or together with the adjacent nitrogen atom represent a pyridyl group which may be unsubstituted or substituted by an alkyl group having l-6 carbon atoms; such as those wherein the pyridyl group is substi tuted at the 2- or 4-position by a methyl group;

Compounds wherein R R or R is a 2-hydroxyethyl or carbethoxy methyl group, or wherein two of said groups together with the nitrogen atom is a piperidinyl group;

Compounds wherein A is a methylene or ethylene group; and

ticnlar, synthetic textile fibres (e. g. cellulose acetate and solutionin water. They may-be used with particular advantage in the whitening, brightening and/or bleaching of cellulose acetate and acrylic fibres, if desired in the presence ofja non-ionic or cationic surface active agent. However the compounds according to the invention are in genei'al incompatible with anionic surface active agents.

' Fibres may be treated with compounds according to the compounds according to the invention show good light stability. The use of compounds according to the invention'in the optical whitening, brightening and/or bleaching'of textile fibres thus enables fabrics made from such tib'res having good whitness and/or brightness to be pro- "It will be understood that the invention also includes a composition for use in the treatment of an at least in part synthetic textile material comprising a compound of the Formula I and a carrier, preferably a liquid carrier such as water. As indicated above, the composition may group,.R .represents a methoxy group at the 5-position of the coumarin group, R R and R each represents a v(wher 311.1322331!" and e e. as e e e a s methyl, ethylfcarbethoxymethyl or z hydrosr eth rgraup=*"" or R R and R together with the adjacent nitrogen atom NR R with a compound of formula R X (wherein represents a pyridyl or lower alkyl substituted (e.g. 2- R represents a substituted or. unsubstituted alkyl group or 4-methyl'pyridyl group, or two of R R a'hdR rep- 5 andX and- ,r 1 .a re hereinbeforejdefined). Ifhe rreae tio n is resent a piperidinyl group. A represents a methylene or 'conveniently'etl' ctejd ge injan organic solvent, for example ethylene and X- represents a halide ion (e.g. a chlorideg alowenalkan e .g .-b 1 '.1t2 1nol advantagepusly at an elevated bromide or iodide ion) or a methosulphate ion. temperature fonexample, under reflux. Again the, X(

Examples of these compounds are f anion of the compound of Formula- 1 first obtained can if Y desiredbelexclianged for'other anionsnj N 3 (7 gthoxycoumann 3 Y1) p henyl] oxadlazql .The compounds ac'cor'ding to the invention may-salsa be prepared by reacting a compoiihd oi formula 5-yl methylpyridinium chloride; N,N,N-trimethyl-N-3[4-(7-ethoxycoumarin-3-yl) a phenyl]-1,2,4eoxadiazol-5-yl-methylammonium iodide; N,N,N-trimethyl-N-3- [4- (7-ethoxycoumarin-3-y1) 1 phenyl]-l,2,4-oxadiazol=5-yl methylammonium- 15 methosulphate; and N,N-bis( Z-hydroxyethyl -N-methy1-N- 3- (4- 7-ethoxycoumarin-3-yl)phenyl)-1,2,4-oxadiazol-5-yl)methyl-, ammonium methosulphate. a

The compounds according to the invention may be prepared by any convenient method. We have found it' convenient, for example, to prepare the compounds 'ac i' cording to the invention by reacting a compound offo rmula r 0 v1,- inio- To j I v a w s (v) Y 5 (whereiiig RfgpR RQAQm, X nare as hereinbefore defined). The reaction :is preferably effected in a solvent, N for example/an aqueous alcoholic solvent, U

I v The Compounds of- FormulalI used in the preparation.

N ;j' of the. compounds ofFormulapI maybe prepared by known N methods for;. example by reacting an arnidoxime of (wherein R R R In andA are as hereinbefore defined Q U w 'r I and X represents a halogen atom) with an amine of'fore mula NR R R (wherein R R and R are as hereinbe fore defined). The reaction is conveniently eifected'in organic solvent, for example in the amine of lformula NR R R if desired in the presence of a co-solvent'sueh 40 v as, for example, a lower alkanol e.g. n-butauoL'In general, I I the reaction is preferably effected at an elevated temper- 0E ature for example at a temperature of l Q F! f, e (wherein R R and R are as hereinbefore defined) with n where e eeeewem 1e used, up w the ref u m e a fii nctional 'deriva ve tears-argue acnzarrs mm amre of the solvent y wI j a X -(A) coH' (vi/herein XLA' alum-are as herein:

The Feactlon of the Compound of FormulalI w i beforedefined). The functional derivativeofstheecarboxthe amme of formula 4 5 q l y. P YQ UW fl ylic acid may, for example, be an acid halide, "eLgJthe conflpound 0f Formula I wherem the Q f 1?, 4 acid chloride, anhydride or amide, Orthoes ters of carboxdeflved m the compound of Formula a J S ylic estei-s. ;may also ;be used tocycli zecomp'ounds c'omcases the reaction is most conveniently used forthe pf pounds of Formula V The compounds of Formula VI aration of Compounds of Formula I wherein ia i may be prepared by known methods, conveniently by reacresents ahalide ion. However, if it is desired to prepare tion f g i l f f m l compounds of Formula I wherein X represents other; than a halide ion, a compound of Formula Lwheriein. X represents a halide ion may be converted into i a; compound of Formula I, wherein X is other than halide ion, by known methods. Such method sj'rna y, sired, also be used for converting a compound ,of mula I wherein X represents one halide i y l other compound of Formula I wherein X different halide ion. I v t 7 Compound of Formula I wherein R R and 'R ogether d ox lamme with the adjacent nitrogen atom represent othertbari an aromatic ring, and in particular those wherein X re resents other than a halide ion, may conveniently be, pie- 65 pared by reacting a compound of formula heremb re-defineM-with,

(wherei V .l

of a thioarnide of: formula v semi; grad ll'ydroxylamine. T he z-thioamidetof- Formula :VIII may "be WithhydrOgensulphide'. we

ei are hereinbef ore defined) prepared, for example by' reaction of a nitrile of Formula The compounds of Formula VII may be prepared, for example, according to the method described in British Pat. No. 1,152,875.

The compounds of Formula III used in the preparation of compounds according to the invention may be prepared by known methods, for example by reacting a compound of Formula V1 with a functional derivative of a carboxylic acid of formula R ACO H (wherein R and A are as hereinbefore defined).

The compounds of Formulae -II, III and VII may also be prepared by reacting a compound'of Formula IV with a diazonium salt of formula (wherein X is as hereinbefore defined and R represents a group of formula 1OL LQJ-ltm or CN wherein A, X and R are as hereinbefore defined).

The following examples are given by way of illustration only. All parts are by weight unless otherwise stated.

EXAMPLE 1 N-{3- [4- (7-ethoxycoumarin-3-yl) phenyl] 1 ,2,4-oxadiazol-S-ylmethyl}pyridinium chloride (a) 3-[4-(5-chloromethyl)-1,2,4 oxadiazol 3 yl] pheny1-7-ethoxycoumarin.-58.2 parts of 3 (4-cyanophenyl)-7-ethoxycoumarin, 27.8 pts. of hydroxylamine hydrochloride, and 29.0 pts. of sodium carbonate were heated in 300 pts. of pyridine on a boiling water bath for 2 hrs. and then poured into 1,000 pts. of cold water. The off-white solid produced was filtered off, washed with water and dried to give 60.3 pts. of 4-(7-ethoxycoumarin- 3-yl)benzamidoxime, m. pt. 220 C. The amidoxime obtained was added to 56.6 pts. of chloroacetyl chloride in 600 pts. of o-dichlorobenzene, stirred 1 hr. at room temperature and then the water distilled off over 2 hrs., the temperature rising to 160 C. The mixture was then refluxed for 4 hrs., cooled and distilled with steam. The solid material was collected and re-crystallized from nbutanol to give 99 pts. of 3-[4-(5-chloromethyl)-1,2,4- oxadiazol 3 yl] 7 ethoxycoumarin as pale yellow crystals, m. pt. 177 C.

(b) 30.6 pts. of 3 [4 (5-chloromethyl)-1,2,4,-oxadiazol-3-yl]phenyl 7 ethoxycoumarin and 90 pts. of pyridine were. heated together at 100 C. for 5 mins., cooled and the solid collected, washed with acetone and recrystallized from methanol to give N-{3-[4-(7-ethoxycoumarin-3-yl)phenyl]-1,2,4 oxadiazol 5 ylmethyl} pyridinium chloride as a very pale cream powder, m. pt. 217 C., )t 348 m E 610. A dilute solution of this compound in water exhibited a blue-violet fluorescence.

EXAMPLE 2 N,N,N-triethyl-N-{3- [4- (7-ethoxycoumarin-3yl phenyl] 1,2,4-oxadiazol-5-yl methyl}ammonium chloride 38.0 parts of 3 [4 (S-chloromethyl)-l,2,4-oxadiazol- 3-yl]phenyl-7-ethoxycoumarin (prepared as in Example 1) in 250 pts. of n-butanol were refluxed with 28 pts. of triethylamine for 5 hrs., cooled and filtered. The filtrate was poured into 1,000 pts. of light petroleum (b .pt. 40- 60 C.) and the precipitated solid was collected and recrystallized from methanol to give N,N,N-triethyl-N- {3-[4-(7-ethoxycoumarin 3 yl)phenyl]-1,2,4oxadiazol- 5-yl}methyl ammonium chloride, m. pt. 214 C., E 660.

6 EXAMPLE 3 N-{3-[4-(7-ethoxycoumarin-3-yl)phenyl]-1,2,4-oxadiazol-5-yl}ethyl pyridinium chloride (a) 3 [4 (5 chloroethyl) 1,2,4-oxadiazol-3-yl] phenyl-7-ethoxycoumarin.-50 parts of 2-chloropropionyl chloride and 30 parts of 4-(7ethoxycoumarin-3-yl)- benzamidoxime (prepared as in Example 1) were heated at C. until the reaction mixture became homogeneous and then maintained at 130 C. for a further 40 mine. The reaction mixture was then poured into 700 parts cold water and the resulting solid was. collected, washed with cold water and recrystallized from acetic acid to give 23 parts of 3-[4-(5-chloroethyl)-1,2,-4 oxadiazol 3 yl] phenyl-7-ethoxycoumarin. The pale yellow crystals melted at 178 (dec.) A 348 mu, E 810.

(b) 8 parts of 3 [4 (S-chIoroethyl)-1,2,4-oxadiazol- 3-yl]phenyl-7-ethoxycoumarin and 15 parts of pyridine were heated to 120130 C. for 90 mins., cooled and poured into 200 parts of acetone. The solid was collected and digested with 200 parts of boiling ethanol. The insoluble material was filtered off and the filtrate was concentrated to small bulk and triturated with acetone. The precipitated solid was recrystallized from n-hutanol to give N {-[4-(7-ethoxycoumarin-3-yl)phenyl]-1,2,4-oxadiazol-5-yl}ethyl pyridinium chloride as a pale cream powder, In. pt. 222224, k 348 m,u, E 620.

EXAMPLE 4 N-{3-[4-(7-ethoxycoumarin-3-yl)phenyl]-1,2,4-oxadiazol- 5-yl}methyl-Z-methylpyridinium chloride N {3 [4 (7-ethoxycoumarin-3-yl)phenyl]-1,2,4- oxadiazol-5-yl}methyl-2 methylpridinium chloride was prepared as a cream powder, m. pt. ZOE-209 C. (EtOH), 348 mu, E 630, in an analogous manner to Ex ample 1 using a-picoline instead of pyridine.

EXAMPLE 5 N-{3-[4-(7-ethoxycoumarin-3-yl)phenyl]-1,2,4-oxadiazol-5-yl}methyl-4-methylpyridinium chloride N {3 [4 (7-ethoxycoumarin-3-yl)phenyl]-1,2,4- oxadiazol 5 yl}methyl-4-methylpyridinium chloride, m. pt. C. (EtOH), 7\,,,,,,, 348-349 m E 640, was

' prepared in an analogous manner to the method of Example 1 using 'y-picoline instead of pyridine.

EXAMPLE 6 N {3-[4-(7-rnethoxycoumarin-3-yl)phenyl]-1,2,4-oxadiazol-5-yl}methylpyridinum chloride (a) 3- [4-(S-chloromethyl-1,2,4-oxadiazol-3-yl)pheny1]- 7-methoxycoumarin.--4.2 parts of 3-(4-aminophenyl)-5- chloromethyl-1,2,4-oxadiazole were dissolved in 12 parts of concentrated hydrochloric acid and 50 parts of water were treated at 20 C. with an aqueous solution of 1.5 parts of sodium nitrite. The resulting diazonium salt was added at 35 C. to a stirred solution of 3.6 parts of 7- methoxycoumarin in 200 parts of acetone containing 0.05 part of quinol and 0.5 part of cuprous chloride in 6 parts of water. After allowing the reaction mixture to stand for 3 hrs. the resulting solid was collected and recrystallized from n-butanol to give 3-[4-(S-chloromethyl-1,2,4-oxadiazol-3-yl)phenyl]-7-methoxycoumarin, m. pt. 220-2 C.

(b) The chloromethyl compound was heated with pyridine as in Example 1.to give N-{3-[4-(7-methoxycoumarin 3 yl)phenyl]-l,2,4-oxadliazol-5-yl}methylpyridinium chloride, pale cream solid, m. pt. 227-9 C. (dec. from butanol/ethanol). A 348 m E 640.

EXAMPLE 7 N {3-[4-(7-hydroxycoumarin-3-yl)phenyl]-1,2-,4-oxadiazo1-5-yl}methylpyridinium chloride 3 [4 (5 chloromethyl) 1,2,4-oxadiazol-3-yl]-7-hydroxycoumarin, m. pt. 250-2 C. (from n-BuOH) was prepared from 7-hydroxycoumarin by an analogous process to that of Example 6(a) and after treatment with pyridine accorded N-{3-[4-(7-hydroxycoumarin-3-yl) phenyl] 1,2,4-oxadiazol-5-yl}methylpyridinum chloride, 111. pt. 265-7 C. (decomp.).

EXAMPLE 8 N,N,N trimethyl-N-{3-[4-(7-ethoxycoumarin-3-y1)phen yl]-1,2,4-oxadiazol-5-yl} methylammonium iodide A mixture of parts of 3-[4-(5-chloromethyl-1,2,4- oxadiazol-3-yl)phenyl]-7-ethoxycoumarin, 12 parts of a 25-30% aqueous solution of dimethylamine and 50 parts butanone was heated to reflux for minutes, cooled and the resulting solid was collected, washed with water and crystallized from n-butanol. A yield of 7.1 parts of 3-[4- (5 dimethylaminomethyl-1,2,4-oxadiazol-3-yl)-phenyl]- 7-ethoxycournarin, 111. pt. 15 8-9 C. was obtained. 3 parts of this compound in parts butanol were refluxed with 1.5 parts of iodomethane for 30 minutes and the resulting pale yellow solid was collected, washed thoroughly with acetone and dried. The yield was 3.9 parts of N,N,N-trimethyl N {3- [4-(7-ethoxycoumarin-3-yl)phenyl]-1,2,4- oxadiazol-5-yl}-methylammonium iodide, m. pt. 221- 3 C. (decomp.). A 349 my, E 560.

EXAMPLE 9 N,N,N trimethyl-N-{3-[4-(7-ethoxycoumarin-3-yl)phenyl] 1,2,4 oxadiazol-S-yl}methylammonium methosulphate By substituting dimethylsulphate for iodomethane in the method of Example 8 were obtained 3.9 parts of the corresponding methosulphate, 111. pt. 242-4 C., A 348-9 mp, E 560.

EXAMPLE 10 N (3-(4-(7-methoxy-4-methylcoumarin-3-yl)phenyl)-l, 2,4-oxadiazol-5-yl)methyD-pyridinium chloride This compound was prepared by the method of Example 1, using 3-(4-cyanophenyl)-7-methoxy-4-methylcoumarin instead of 3-(4-cyanophenyl)-7-ethoxy-coumarin.

M. pt. 263-4 C.

A 358 mu, E 644.

EXAMPLE 11 N-( 3- (4- 5,7-dimethoxy coumarin-3-yl)phenyl)-1,2,4-oxadiazol-S-yl) methyl)-pyridinium chloride This compound was prepared by the method of Example 1, using 3-(4-cyanophenyl)-5,7-dimethoxy coumarin.

M. pt. 218-221 C. (decomp.).

)t 358 my, E 644.

EXAMPLE 12 N carbethoxymethyl N,N-dimethyl-N-(3-(4-(7-ethoxycoumarin 3 yl)phenyl)-1,2,4-oxadiazol-5-yl)methylammonium bromide This compound was prepared by the method of Example 8, using ethyl bromoacetate instead of iodomethane.

Yield 3.5 parts.

M. pt. 180 C.

A 348 mu, E 562.

EXAMPLE 13 N 2 Hydroxyethyl N-(3-(4-(7-ethoxycoumarin-3-yl) phenyl) 1,2,4 oxadiazol 5 yl)methyl piperidinium chloride then diluted with acetone and cooled. The solid was collected, washed with acetone and petroleum ether and dried. The yield was 5 pts. of title compound.

M. pt. 202 C.

A 348-9 ma, E 695.

EXAMPLE 14 N,N dimethyl N 2 hydroxyethyl N (3 (4-(7- ethoxycoumarin 3 yl)phenyl) 1,2,4-oxadiazol-5-yl) methyl ammonium chloride 5 parts of 3 (4 (5 dimethylaminomethyl-1,2,4- oxadiazol-3-yl) pheny1)-7-ethoxycoumarin (prepared as in Example 8) and 20 parts of 2-chloroethanol were refluxed for 8 hours, cooled and the reaction mixture diluted with acetone. The solid was collected, washed with acetone and petroleum spirit and dried. The yield was 2.4 parts of title compound.

M. pt. 198 0. A 348 mp, E11 640.

EXAMPLE l5 N,N-Bis(2 hydroxyethyl)-N-methyl-N-( 3 (4 (7- ethoxy-coumarin 3 yl)phenyl) 1,2,4 oxadiazol-S- yl)methyl ammonium methosulphate 8 parts 3 (4 (5 chloromethyl-1,2,4-oxadiazol-3-yl) phenyl) 7 ethoxycoumarin, 5 parts 87% aqueous so lution of diethanolamine, and 40 parts butanone were refluxed for 1 hour, cooled, and the solid collected and recrystallized from n-butanol. There were thus obtained 8.5 parts of 3-(4-(5-bis(2-hydroxyethyl)-aminomethyl-1, 2,4-oxadiazo1 3 yl)-7-ethoxy)coumarin, 111. pt. 1746 C. 6 parts of this compound were refluxed in 60 parts butanone with 3 parts dimethyl sulphate for 4 hours, the reaction mixture cooled and the solid collected, Washed with acetone and dried, to give a yield of 6 parts title compound.

M. pt. 231-4 C. (decomp.). A 349 m E 530.

EXAMPLE l6 Scoured polyacrylonitrile fibres were introduced into an aqueous bath (liquor:goods ratio 40:1) at 60 C. and they were treated with the compound of Example 1 (0.1- 0.3% by weight of fibres), a non-ionic dispersing agent (0.5% by weight of fibres), 0.4 g./l. phosphoric acid (pH 2.5), 0.6 g./l. sodium chlorite and 0.5-1.0 g./l. sodium nitrate. The temperature was raised to C. for 30 mins., maintained for 30 mins. at this temperature and then cooled to 50 C. The fibres were rinsed thoroughly and given an anti-chlor treatment of 1.0 g./l. sodium bisulphite and 1.0 g./l. sodium bicarbonate at 60 C. for 20 mins. The rinsed fibres exhibited a brilliant whiteness.

EXAMPLE 17 Cellulose triacetate fibres were treated in an aqueous bath (liquorz goods ratio 40:1) at 60 C. with the compound of Example 1 (OJ-0.3% by weight of fibres), a nonionic dispersing agent (0.5% by weight of fibres), 0.5 g./l. formic acid (pH 4), 2 g./l. sodium chlorite and 2 g./l. sodium nitrate. The temperature was raised to 95 C. for 30 mins., maintained for 30 mins. at this temperature and then cooled to 50 C. The fibres were rinsed thoroughly and given an anti-chlor treatment of 1 g./l. sodium bisulphite at 60 C. for 20 mins. After rinsing, the fibres exhibited a brilliant whiteness.

We claim:

1. A compound of the formula:

wherein:

R is hydrogen or a lower alkyl group having 1-6 carbon atoms;

R; is hydrogen or a lower alkyl group having 1-6 carbon atoms;

R is hydrogen, halogen or a lower alkyl or alkoxy group containing 1-6 carbon atoms;

R R and R are the same or dilferent and each is a lower alkyl group having 1-6 carbon atoms or a lower alkyl group having 1-6 carbon atoms substituted by hydroxy, carbethoxy, or carboxy; or

R R and R together with the adjacent nitrogen atom form a pyridine ring or a pyridine ring substituted by an alkyl group having 1-6 carbon atoms; or two of R R or R together with the adjacent nitrogen atom form a piperidine ring or a piperidine ring substituted by an alkyl group having 1-6 carbon atoms with the remaining R R or R group being a lower alkyl group having 1-6 carbon atoms or a lower alkyl group substituted by hydroxy, carbethoxy, or carboxy;

A is an alkylene group having l-6 carbon atoms or a monocyclic arylene group;

m is or 1;

X is the anion of an organic or inorganic acid; and

n is the valency of the anion.

2. A compound as claimed in claim 1 wherein R is a methyl or ethyl group.

3. A compound as claimed in claim 1 wherein R is a methyl group.

4. A compound as claimed in claim 1 wherein R is a methoxy group.

5. A compound as claimed in claim 1 wherein R R and R each is a methyl or ethyl group, or together with the adjacent nitrogen atom represent a pyridyl group which may be unsubstituted or substituted by an alkyl group having 1-6 carbon atom.

6. A compound as claimed in claim 5 wherein the pyridyl group is substituted at the 2- or 4-position by a methyl group.

7. A compound as claimed in claim 1 wherein R R or R is a Z-hydroxyethyl or carbethoxy methyl group, or wherein two of said groups together with the nitrogen atom is a piperidinyl group.

8. A compound as claimed in claim 1 wherein A is a methylene or ethylene group.

9. A compound as claimed in claim 1 wherein X is a halide or methosulphate ion.

10. A compound as claimed in claim 1, said compound being N 3 [4-(7-ethoxycoumarin-3-yl)phenyl]-1,2,4- oxadiazol-5-yl methylpyridinium chloride.

11. A compound as claimed in claim 1, said compound being N,N,N-trimethyl-N 3-[4-(7-ethoxycoumarin-3-yl) phenyl] 1,24 oxadiazol 5 yl methylammonium iodide.

12. A compound as claimed in claim 1, said compound being N,N,N trimethyl-N-3-[4-(7-ethoxycoumarin-3-yl) phenyl] 1,2,4 oxadiazol-S-yl methylammonium methosulphate.

13. A compound as claimed in claim 1, said compound being N,N bis(2 hydroxyethyl)-Nmethyl-N-(3-(4-(7- ethoxycoumarin 3 yl)phenyl) 1,2,4-oxadiazo1-5-yl) methyl ammonium methosulphate.

References Cited UNITED STATES PATENTS 3,245,989 4/1966 Palazzo 260-247.2 3,444,180 5/1969 Maeder et a1 26030'7 3,655,684 4/1972 Osbond et a1 260-307 G 3,708,475 1/1973 Kirchmayr 260--24O C HENRY R. JILES, Primary Examiner G. T. TODD, Assistant Examiner US. Cl. X.R.

260-295 F, 307 G, 343.2; 252543, 301.2 W 

